Highly efficient K-Fe/C catalysts derived from metal-organic frameworks towards ammonia synthesis

被引:36
作者
Yan, Pengqi [1 ,2 ,3 ]
Guo, Wenhan [4 ]
Liang, Zibin [4 ]
Meng, Wei [4 ]
Yin, Zhen [5 ]
Li, Siwei [1 ,2 ,3 ]
Li, Mengzhu [1 ,2 ,3 ]
Zhang, Mengtao [1 ,2 ,3 ]
Yan, Jie [1 ,2 ,3 ]
Xiao, Dequan [6 ]
Zou, Ruqiang [4 ]
Ma, Ding [1 ,2 ,3 ]
机构
[1] Peking Univ, Beijing Natl Lab Mol Sci, Coll Chem & Mol Engn, Beijing 100871, Peoples R China
[2] Peking Univ, Coll Engn, Beijing 100871, Peoples R China
[3] Peking Univ, BIC ESAT, Beijing 100871, Peoples R China
[4] Peking Univ, Beijing Key Lab Theory & Technol Adv Battery Mat, Dept Mat Sci & Engn, Coll Engn, Beijing 10087, Peoples R China
[5] Tianjin Polytech Univ, State Key Lab Separat Membranes & Membrane Proc, Sch Chem & Chem Engn, Tianjin 300387, Peoples R China
[6] Univ New Haven, Dept Chem & Chem Engn, West Haven, CT 06516 USA
基金
中国国家自然科学基金;
关键词
metal-organic frameworks; pyrolysis; ammonia synthesis; iron nanoparticles; K promotion; NITROGEN-FIXATION; IRON CATALYST; ACTIVE-CARBON; REDUCTION; BARIUM; N-2; MOLECULES; CHEMISTRY; PROGRESS;
D O I
10.1007/s12274-019-2349-0
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Fe-based catalysts have been discovered as the best elementary metal-based heterogeneous catalysts for the ammonia synthesis in industrial application during the last century. Herein, a novel and scalable strategy is developed to prepare the K-promoted Fe/C catalyst with extremely high Fe loading (> 50 wt.%) through pyrolysis of the Fe-based metal-organic framework (MOF) xerogel. The obtained K-Fe/C catalysts exhibited superior activity and stability towards ammonia synthesis. The weight-specific reaction rate of Fe/C with K2O as promoter can achieve 12.4 mmol center dot g(-1)center dot h(-1) at 350 degrees C and 30.4 mmol center dot g(-1)center dot h(-1) at 400 degrees C, approximately four and two times higher than that of the commercial fused-iron catalyst (3.4 mmol center dot g(-1)center dot h(-1) at 350 degrees C and 16.7 mmol center dot g(-1)center dot h(-1) at 400 degrees C) under the same condition, respectively. The excellent performance of K-Fe/C can be ascribed to the inherited structure derived from the metal-organic frame precursors and the promotion of potassium, which can modify the binding energy of reactant molecules on the Fe surface, transfer electrons to iron for effective activation of nitrogen, prevent agglomeration of Fe nanoparticle (NPs) and restrain side reaction of carbon matrix to methane.
引用
收藏
页码:2341 / 2347
页数:7
相关论文
共 34 条
[1]  
Appl M., 2007, AMMONIA, P9
[2]   A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia [J].
Arashiba, Kazuya ;
Miyake, Yoshihiro ;
Nishibayashi, Yoshiaki .
NATURE CHEMISTRY, 2011, 3 (02) :120-125
[3]   High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture [J].
Banerjee, Rahul ;
Phan, Anh ;
Wang, Bo ;
Knobler, Carolyn ;
Furukawa, Hiroyasu ;
O'Keeffe, Michael ;
Yaghi, Omar M. .
SCIENCE, 2008, 319 (5865) :939-943
[4]   A Synthetic Single-Site Fe Nitrogenase: High Turnover, Freeze-Quench 57Fe Mossbauer Data, and a Hydride Resting State [J].
Del Castillo, Trevor J. ;
Thompson, Niklas B. ;
Peters, Jonas C. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (16) :5341-5350
[5]   PRIMARY STEPS IN CATALYTIC SYNTHESIS OF AMMONIA [J].
ERTL, G .
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A-VACUUM SURFACES AND FILMS, 1983, 1 (02) :1247-1253
[6]   Molecules at Surfaces: 100 Years of Physical Chemistry in Berlin-Dahlem [J].
Ertl, Gerhard .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (01) :52-60
[7]   The Chemistry and Applications of Metal-Organic Frameworks [J].
Furukawa, Hiroyasu ;
Cordova, Kyle E. ;
O'Keeffe, Michael ;
Yaghi, Omar M. .
SCIENCE, 2013, 341 (6149) :974-+
[8]   Ammonia synthesis with barium-promoted iron-cobalt alloys supported on carbon [J].
Hagen, S ;
Barfod, R ;
Fehrmann, R ;
Jacobsen, CJH ;
Teunissen, HT ;
Chorkendorff, I .
JOURNAL OF CATALYSIS, 2003, 214 (02) :327-335
[9]   Promotion of Nb2O5 on the wustite-based iron catalyst for ammonia synthesis [J].
Han, Wenfeng ;
Huang, Shiliang ;
Cheng, Tianhong ;
Tang, Haodong ;
Li, Ying ;
Liu, Huazhang .
APPLIED SURFACE SCIENCE, 2015, 353 :17-23
[10]   Prevalence of Bimolecular Routes in the Activation of Diatomic Molecules with Strong Chemical Bonds (O2, NO, CO, N2) on Catalytic Surfaces [J].
Hibbitts, David ;
Iglesia, Enrique .
ACCOUNTS OF CHEMICAL RESEARCH, 2015, 48 (05) :1254-1262